CN109529876A - With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase - Google Patents
With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase Download PDFInfo
- Publication number
- CN109529876A CN109529876A CN201811569530.2A CN201811569530A CN109529876A CN 109529876 A CN109529876 A CN 109529876A CN 201811569530 A CN201811569530 A CN 201811569530A CN 109529876 A CN109529876 A CN 109529876A
- Authority
- CN
- China
- Prior art keywords
- porous
- excoyoz
- nipd
- nanocatalyst
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 108090000698 Formate Dehydrogenases Proteins 0.000 title claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 235000019253 formic acid Nutrition 0.000 claims abstract description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004280 Sodium formate Substances 0.000 claims abstract description 9
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 108090000854 Oxidoreductases Proteins 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910000085 borane Inorganic materials 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000007357 dehydrogenase reaction Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
Abstract
The invention discloses a kind of methods with NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase, belong to technical field of chemistry and chemical engineering.This method step is: the NiPd/ porous C exCoyOz nanocatalyst prepared is placed in reactor, reactor is placed in water-bath and rises to certain temperature, then formic acid and sodium formate mixed liquor are added in reactor and are reacted, the hydrogen of generation is collected using drainage.Unlike existing catalyst: according to the present invention, adjusting W metal in catalyst, the high activity for formate dehydrogenase hydrogen, highly selective, high stability nanocatalyst can be made in the molar ratio of mole when support precursor cerous nitrate, cobalt nitrate and 2-methylimidazole of Pd.Formate dehydrogenase reaction is carried out using the catalyst, conversion rate of dehydrogenation and selectivity are 100%, and the TOF value of reaction is greater than 420h‑1, 3h is recycled, the TOF value of reaction is still greater than 414h‑1。
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to be catalyzed with NiPd/ porous C exCoyOz nanocatalyst
The method of formate dehydrogenase.
Background technique
Formic acid (HCOOH) is the hotter novel chemical hydride of current research, it has chemical property mild, under room temperature
For liquid, existing fossil energy device can be utilized well, be known as most promising hydrogen fuel cell Hydrogen Energy supply
One of material.
For formic acid as hydrogen storage material, efficiently releasing hydrogen includes two kinds of paths: a kind of Direct Dehydration, which decomposes, generates water and an oxygen
Change carbon, wherein carbon monoxide easily causes the poisoning of fuel-cell catalyst；It is another that hydrogen and dioxy are generated by dehydrogenation
Change carbon, is that ideal Hydrogen Energy discharges approach, the control for two kinds of paths, key is to develop efficient formate dehydrogenase catalysis
Agent.
Xu Qiang et al.(Journal of the American Chemical Society 2011,133
(31): 11822-11825) report has synthesized the immobilized AuPd catalyst in MOFs for the first time, which shows excellent urge
Change performance, further discloses the synergistic effect between catalyst activity component, the report of the research opens formic acid as hydrogen storage material
The research boom of material.It is that noble metal, reserves are limited in view of two kinds of metals of Au, Pd, how reduces bullion content while improving
The catalytic activity of catalyst is the hot spot of current research.
Summary of the invention
NiPd/ porous C exCoyOz nano-catalytic is used in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of
The method that agent is catalyzed formate dehydrogenase, realizes first to the NiPd/ porous C exCoyOz nanocatalyst under the conditions of relatively mild
The complete dehydrogenation of acid, and there is good catalytic activity, selectivity and stability.
The technical solution adopted by the present invention to solve the technical problems is as follows.
The NiPd/ porous C exCoyOz nanocatalyst prepared is placed in reactor, reactor is placed in water-bath
Rise to 25~60 DEG C, be then 1:(1.3~2.1 by molar ratio) formic acid and sodium formate mixed liquor be added in reactor carry out it is anti-
It answers, obtains hydrogen product；The catalyst and mixed liquor mass ratio is 1:(40~80).
The NiPd/ porous C exCoyOz nanocatalyst includes Ni, Pd and porous C exCoyOz, wherein the source Ni
In nickel nitrate, Pd derives from potassium chloropalladate, and porous C exCoyOz forms Ce-Co- by cerous nitrate, cobalt nitrate and 2-methylimidazole
MOF roasting is made, and the molar ratio of nickel nitrate and potassium chloropalladate is 1:(0.05~0.25)；Nickel nitrate and cerous nitrate, cobalt nitrate, 2-
The molar ratio of methylimidazole is 1:(1~2.5): (3~8): (12~20).
The NiPd/ porous C exCoyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, cobalt nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, at 26~31 DEG C
It is lower stirring 16~for 24 hours, centrifugation obtain Ce-Co-MOF；
(2) Ce-Co-MOF is transferred to tube furnace, roasting obtains porous C exCoyOz；
(3) the porous C exCoyOz that roasting obtains is placed in nickel nitrate and potassium chloropalladate solution, uses ammonia boron at 2~8 DEG C
Alkane 2~4.5h of solution reduction, centrifugal drying obtain NiPd/ porous C exCoyOz nanocatalyst.
In the preparation step (2) of the NiPd/ porous C exCoyOz nanocatalyst: tube furnace maturing temperature be 490~
545 DEG C, 4~7.5h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 15%~21%.
In the preparation step (3) of the NiPd/ porous C exCoyOz nanocatalyst: ammonia borane concentration be 0.08~
0.16mol/L。
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention uses immersion reduction method synthetic catalyst that is easy to operate, being easy to industrial applications, catalyst carrier
Preparation is presoma using cerous nitrate cheap and easy to get, cobalt nitrate and 2-methylimidazole, and it is molten to be dissolved in methanol by certain mol proportion
Uniform solution is formed in liquid, reacts certain time under mild reaction conditions, centrifugation obtains Ce-Co-MOF, by Ce-Co-MOF
It is transferred to tube furnace, roasting obtains porous C exCoyOz under certain roasting condition and atmosphere, roasting is obtained porous
CexCoyOz is placed in the nickel nitrate and potassium chloropalladate solution of definite composition, restores one section using ammonia Borane solution in a mild condition
Time, centrifugal drying obtain the NiPd/ porous C exCoyOz nanocatalyst with high dispersancy nano particle.
2, catalyst prepared by the present invention is to formate dehydrogenase reaction activity, selectivity and stability with higher.It uses
The catalyst can realize formate dehydrogenase under temperate condition, and conversion rate of dehydrogenation and selectivity are 100%, and the TOF value of reaction is greater than
420h-1, 3h is recycled, the TOF value of reaction is still greater than 414h-1。
Specific implementation method
The present invention is described in further details below by embodiment.But the example is not constituted to limit of the invention
System.
Embodiment 1
Prepare catalyst process
1mmol cerous nitrate, 8mmol and 12mmol 2-methylimidazole are dissolved in be dissolved in 200mL methanol formed it is uniform molten
Liquid stirs for 24 hours at 26 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, in 490 DEG C of calcining times
7.5h, calcination atmosphere 21%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in containing 1mmol
In nickel nitrate and 0.05mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.08mol/L in 8 DEG C of reduction 4.5h, obtain
Catalyst is denoted as NiPd0.05/ porous C e1Co8Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 25 DEG C, formic acid and sodium formate mixed liquor 2g that molar ratio is 1:2.1 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 450h-1, 3h is recycled, reaction
TOF value is still greater than 446h-1。
Embodiment 2
Prepare catalyst process
2.5mmol cerous nitrate, 3mmol and 20mmol 2-methylimidazole are dissolved in be dissolved in 200mL methanol formed it is uniform molten
Liquid, stirs 16h at 31 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, in 545 DEG C of calcining times
4h, calcination atmosphere 15%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in nitre containing 1mmol
In sour nickel and 0.25mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.16mol/L in 2 DEG C of reductase 12 h, catalysis is obtained
Agent is denoted as NiPd0.25/ porous C e2.5Co3Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 60 DEG C, formic acid and sodium formate mixed liquor 4g that molar ratio is 1:1.3 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 640h-1, 3h is recycled, reaction
TOF value is still greater than 635h-1。
Embodiment 3
Prepare catalyst process
2mmol cerous nitrate, 7mmol and 15mmol 2-methylimidazole are dissolved in be dissolved in 200mL methanol formed it is uniform molten
Liquid, stirs 18h at 28 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, in 535 DEG C of calcining times
6h, calcination atmosphere 18%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in nitre containing 1mmol
In sour nickel and 0.2mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.12mol/L in 6 DEG C of reduction 3.5h, catalysis is obtained
Agent is denoted as NiPd0.2/ porous C e2Co7Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 30 DEG C, formic acid and sodium formate mixed liquor 3g that molar ratio is 1:1.9 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 525h-1, 3h is recycled, reaction
TOF value is still greater than 521h-1。
Embodiment 4
Prepare catalyst process
1.5mmol cerous nitrate, 4mmol and 17mmol 2-methylimidazole are dissolved in be dissolved in 200mL methanol formed it is uniform molten
Liquid, stirs 23h at 29 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, in 520 DEG C of calcining times
5.5h, calcination atmosphere 16%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in containing 1mmol
In nickel nitrate and 0.15mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.14mol/L in 6 DEG C of reduction 3.5h, obtain
Catalyst is denoted as NiPd0.15/ porous C e1.5Co4Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 40 DEG C, formic acid and sodium formate mixed liquor 2.4g that molar ratio is 1:1.7 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 574h-1, 3h, reaction is recycled
TOF value be still greater than 568h-1。
Embodiment 5
Prepare catalyst process
2.5mmol cerous nitrate, 3mmol and 16mmol 2-methylimidazole are dissolved in be dissolved in 200mL methanol formed it is uniform molten
Liquid, stirs 22h at 31 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, in 490 DEG C of calcining times
6.5h, calcination atmosphere 18%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in containing 1mmol
In nickel nitrate and 0.23mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.10mol/L in 3 DEG C of reductase 12 .5h, obtain
Catalyst is denoted as NiPd0.23/ porous C e2.5Co3Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 45 DEG C, formic acid and sodium formate mixed liquor 3.2g that molar ratio is 1:2.1 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 667h-1, 3h, reaction is recycled
TOF value be still greater than 662h-1。
Embodiment 6
Prepare catalyst process
2mmol cerous nitrate, 5mmol and 12mmol 2-methylimidazole are dissolved in be dissolved in 200mL methanol formed it is uniform molten
Liquid, stirs 21h at 29 DEG C, and centrifugation obtains Ce-Co-MOF, Ce-Co-MOF is transferred to tube furnace, in 535 DEG C of calcining times
4.5h, calcination atmosphere 21%O2/N2, roast and porous C exCoyOz be made, porous C exCoyOz obtained is placed in containing 1mmol
In nickel nitrate and 0.09mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.13mol/L in 7 DEG C of reduction 3.5h, obtain
Catalyst is denoted as NiPd0.09/ porous C e2Co5Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 60 DEG C, formic acid and sodium formate mixed liquor 3.5g that molar ratio is 1:1.8 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 620h-1, 3h, reaction is recycled
TOF value be still greater than 614h-1。
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from present inventive concept, several simple deductions and replacement can also be made, all shall be regarded as belonging to the present invention by institute
Claims of submission determine the protection scope of patent.
Claims (3)
1. with the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase, it is characterised in that: by what is prepared
NiPd/ porous C exCoyOz nanocatalyst is placed in reactor, and reactor is placed in water-bath and rises to 25~60 DEG C, then will
Molar ratio be 1:(1.3~2.1) formic acid and sodium formate mixed liquor be added reactor in reacted, obtain hydrogen product；
The catalyst and mixed liquor mass ratio is 1:(40~80)；
The NiPd/ porous C exCoyOz nanocatalyst includes Ni, Pd and porous C exCoyOz, wherein Ni derives from nitre
Sour nickel, Pd derive from potassium chloropalladate, and porous C exCoyOz forms Ce-Co-MOF by cerous nitrate, cobalt nitrate and 2-methylimidazole and roasts
It fires, the molar ratio of nickel nitrate and potassium chloropalladate is 1:(0.05~0.25)；Nickel nitrate and cerous nitrate, cobalt nitrate, 2- methyl
The molar ratio of imidazoles is 1:(1~2.5): (3~8): (12~20)；
The NiPd/ porous C exCoyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, cobalt nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, stirred at 26~31 DEG C
Mix 16~for 24 hours, centrifugation obtains Ce-Co-MOF；
(2) Ce-Co-MOF is transferred to tube furnace, roasting obtains porous C exCoyOz；
(3) the porous C exCoyOz that roasting obtains is placed in nickel nitrate and potassium chloropalladate solution, it is molten using ammonia borine at 2~8 DEG C
Liquid reductase 12~4.5h, centrifugal drying obtain NiPd/ porous C exCoyOz nanocatalyst.
2. as described in claim 1 with the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase, feature
Be, in the preparation step (2) of the NiPd/ porous C exCoyOz nanocatalyst: tube furnace maturing temperature be 490~
545 DEG C, 4~7.5h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 15%~21%.
3. as described in claim 1 with the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase, feature
Be, in the preparation step (3) of the NiPd/ porous C exCoyOz nanocatalyst: ammonia borane concentration be 0.08~
0.16mol/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811569530.2A CN109529876A (en) | 2018-12-21 | 2018-12-21 | With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811569530.2A CN109529876A (en) | 2018-12-21 | 2018-12-21 | With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109529876A true CN109529876A (en) | 2019-03-29 |
Family
ID=65856212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811569530.2A Withdrawn CN109529876A (en) | 2018-12-21 | 2018-12-21 | With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109529876A (en) |
-
2018
- 2018-12-21 CN CN201811569530.2A patent/CN109529876A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105170169B (en) | A kind of nitrogen-doped graphene iron-based nano-particles reinforcement type catalyst and preparation method thereof | |
| CN106694008B (en) | With support type RhNi/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| Imamura et al. | Electrochemical membrane cell for NH 3 synthesis from N 2 and H 2 O by electrolysis at 200 to 250 C using a Ru catalyst, hydrogen-permeable Pd membrane and phosphate-based electrolyte | |
| CN108311154A (en) | One kind being used for CO2The modification of the novel nickel-base catalyst of methanation and preparation method | |
| CN106672899B (en) | Use RhNiFe/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN109529935A (en) | With the method for Pd@CoO-CNx core-shell catalyst catalysis formaldehyde dehydrogenation | |
| AU2021101698A4 (en) | A Method For Catalyzing The Dehydrogenation Of Formic Acid With NiPd/porous CexCoyOz Nano Catalyst | |
| CN109622009A (en) | With Pd@CeO2-CNxThe method of core-shell catalyst catalysis formaldehyde dehydrogenation | |
| CN101632929A (en) | Hydrogen production catalyst with high-temperature methyl alcohol water vapour and preparation method thereof | |
| CN106694020A (en) | Method for catalyzing hydrazine hydrate dehydrogenation by using supported Rh/CeO2@C3N4 nano-catalyst | |
| CN109225295A (en) | A kind of nitrogenous nickel-base alloy loaded catalyst in surface and preparation and application | |
| CN106744677A (en) | Use RhNiCo/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN103816913A (en) | Catalyst for preparing synthetic gas by reforming of methane and carbon dioxide as well as preparation method and application of catalyst | |
| CN111584884A (en) | Microwave preparation method of fuel cell binary alloy catalyst | |
| CN113278995A (en) | Method for preparing oxalic acid from carbon dioxide or bicarbonate or carbonate | |
| CN109659576A (en) | Micro-nano cell catalyst and preparation method and purposes | |
| CN109529878A (en) | With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase | |
| CN109529876A (en) | With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formate dehydrogenase | |
| CN1680027A (en) | Copper-base catalyst of methanol steam reintegrating hydrogen manufacturing and preparation thereof | |
| CN109499584A (en) | With the method for NiPd/ porous C exCoyOz nanocatalyst catalysis formaldehyde dehydrogenation | |
| CN116474811A (en) | High-efficiency bimetallic catalyst and application thereof in ammonia borane alcoholysis hydrogen production | |
| CN109433226A (en) | With the method for NiAgPt/ porous C exCoyOz nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| CN114229792B (en) | Method and device for preparing hydrogen by catalyzing hydrazine decomposition by nickel-iridium-based supported catalyst | |
| CN110256230A (en) | Efficient catalytic glycerol prepares catalyst of glyceric acid and preparation method thereof under the conditions of a kind of alkali-free | |
| CN109665493A (en) | With the method for NiPd/ porous C exCuyOz nanocatalyst catalysis formaldehyde dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190329 |